Hydrogel networks are of broad scientific interest due to their utility and compatibility in a variety of applications including tissue scaffolds, encapsulation matrices, delivery agents, and separation membranes. Numerous methods to produce hydrogel networks have been reported, generally exploiting physical or chemical cross-linking of hydrophilic polymers and monomers in solution. However, conventional systems like these based on spatially random or statistical crosslinking mechanisms can suffer from weakly-defined network structures with a large distribution of mesh sizes arising from the random nature of the cross-linking process. Heterogeneity in structure and mesh size across the sample profile can result in spatial inconsistencies in mechanical properties, swelling, and mass transport within the hydrogel. As such, there is a long-felt, but unmet need for hydrogel systems that do not exhibit heterogeneity in the structure and mesh size within the hydrogel.